Treatment of textile materials



Patented Nov. 26, 1935 PATENT OFFICE TREATMENT OF TEXTILE MATERIALS George Holland Ellis and-John Allan, Spondon, near Derby, England, assignors to Celanese Corporation of America, a. corporation of Delaware No Drawing.

Application February 16, 1932,

Serial No. 593,408. In Great Britain April 1, 1931 3 Claims.

This invention relates to the colouration of textile materials and more particularly to the production of coloured pattern effects on textile materials.

As is known pattern effects may be produced on textile materials by applying a ground colouration and then printing with a discharge composition containing a discharging agent which will destroy the ground colour in the printed areas. Alternatively, the discharge composition may be applied prior to the application of the ground colour so that fixation of the ground colour is prevented or resisted in the printed areas. Both of these methods may be modified by incorporating in the discharge composition a colouring matter having afiinityfor or capable of being fixed on the materials, and which is resistant to the discharging agents, and coloured pattern effects thereby obtained on coloured grounds. I

A very large number of colouring matters are dischargeable by metallic aldehyde or ketone sulphoxylates, which are hereinafter termed simply sulphoxylates. We have observed that of these colouring matters a considerable proportion are also dischargeable by stannous salts, while many others resist the action of stannous salts sufiiciently well to permit their use for colouring stannous salt discharges. We have found that an exceedingly wide range of very valuable pattern effects may be obtained by printing dyed materials, the colour 'of which is dischargeable both by sulphoxylates and stannous salts, with both a sulphoxylate discharge composition and a stannous salt discharge composition so that one print overlaps the other, at least one of the discharge compositions containing a colouring matter resistant thereto but dischargeable by the other. The term cover printing will hereinafter be used to indicate the operation of printing a pattern overlapping that of a previous printing operation.

Thus for example a cellulose acetate fabric dyed with a blue ground colour which is discompositions.

ing, a material is obtained having a blue ground colouron which appears a green and yellow pattern,- the green being discharged in the places where it overlaps the yellow.

Instead of sulphoxylates on the one hand and on the other stannous compounds, other combinations of discharging agents may be employed in producing pattern effects in accordance with the present invention, providing that one discharging agent is capable of discharging colouring matters which are not discharged by the other. Thus for example not only may reducing discharges be employed in accordance with the present invention, but oxidation discharges may also be employed. If desired, more than two discharging agents may be employed and a still wider range of pattern effects obtained.

Further, in producing the pattern eifects, the ground colour may be applied to or produced on the material after the application of the discharge In such cases the compositions act as discharge-resists? in that they resist" the colouration of the materials in the printed areas by the ground colour. Thus for example the materials may be printed with the discharge compositions and then the ground colour applied. so that only the unprinted areas arecoloured thereby. The term discharging is therefore used as including not only the destruction of an already applied colour but as including preventing the fixation or production of a colour on the materials. charge and discharging are used throughout the description and claims as including resist and resisting respectively.

Again, instead of printing on the discharge compositions, they may be applied by any other convenient method of local application, for example by stencilling. Wherever reference is made to printing in this application it is to be understood that other methods of local application may be substituted if desired. Furthermore, yarn may be impregnated with one of the discharging or resist agents and then woven with untreated yarn to form a fabric which may then be overprinted with a composition containing another discharging agent before or after the application of the dischargeable ground colour.

The ground colour dischargeable by the discharging agents may be applied in any desired way, for instance by dyeingor by padding, printing or other mode of mechanical impregnation. It may be applied uniformly to the materials, or, if desired, locallyby printing, stencilling or other It is to be understood that the terms dis-.

wool, or like materials, or materials containing these fibres in conjunction with cellulose derivative fibres. Further in the case of mixed materials the components may be coloured in solid or contrasting shades or one component may be coloured and another left uncoloured, according to their respective aflinities for the dyestuffs used. a

In carrying out the new process any suitable discharging agents may be employed; Among the more powerful discharging agents metal aldehyde or ketone sulphoxylates may be mentioned, e. g. the sodium or zinc compounds. The zinc compounds are of especial value in the treatment of cellulose ester' or ether materials. As discharging agents exercising a milder discharging action especial mention may be made of stannous salts such for example as stannous chloride, stannous chloracetate, stannous acetate, stannous thiocyanate, or other stannous salts or double salts, which may be acid, neutral, or basic. Again, in the case of an aniline black ground colouration or other colouration produced by oxidation of an aromatic amine on the material, an alkaline substance and/or one of the above or other reducing agents may be used to produce resist effects. Discharging or resist agents may be produced by interaction of suitable compounds in the pastes or other vehicle in which the agents are to be applied to the textile materials, or they may be produced in separate operations as may be desired or convenient.

The discharge or resist compositions may be made up with any desired thickening agents to fit them for application by printing or other means of local application. Again they may contain substances which facilitate the action of the discharging agent, for example anthraquinone in the case of sulphoxylate discharges. Further when colouring materials made of or containing cellulose acetate or other organic derivatives of cellulose, the compositions may with advantage contain swelling agents for the materials, for example thiocyanates, hydroquinone or other phenols, or alcohols.

It will be appreciated that the selection of the discharging agents for use in any particular case will depend upon the nature of the efiects it is required to produce and upon the character of the materials to be coloured. In the case ofmaterials made of or containing cellulose acetate or other cellulose esters or ethers particularly satisfactory results may be obtained by the use of zinc formaldehyde sulphoxylate in one discharge preparation and of a stannous salt in another, particularly stannous chlorothiocyanate or stannous chloride or other stannous salt in conjunction with a thiocyanate in the manner described in U. S. application S. No. 479,087 filed August 30, 1930.

The new process admits of many variations both in respect of the types of discharging agents and of the types of colouring matters utilized.

.hyde sulphoxylate discharge with or without In consequence a very large variety of pattern effects may be obtained.

Still further variations in the efiects may be obtained by first printing with a composition, containing or not a dyestulf having afiinity for the 5 material, and comprising an oxidizing or other agent which will prevent one or more of the sulphoxylate, stannous or other discharge compositions taking efiect in the printed areas.

Again, the fabrics to be treated may comprise 10 undyed yarn and yarn dyed with dyestuifs dischargeable by the discharging agents, or may comprise difierently coloured yarns at least one of the colours being dischargeable by the discharging agents. Still other efiects may be ob- 15 tained by making the fabric from yarn made up of filaments some of which are undyed and some of which are dyed with a dyestuff dischargeable by the discharging agents.

According to a modification of the invention 20 the excess discharging agent of one composition may be destroyed, e. g. by steaming and/ or ageing, after effecting discharge but before the application of a further discharge composition. Thus for example, if in the previously given specific ex- 25 ample of the production of a green and yellow pattern on a blue ground, the material is aged after the application of the zinc formaldehyde sulphoxylate preparation containing the yellow colouring matter but prior to the application of 30 the stannous salt preparation containing the green colouring matter, the green pattern is superimposed on the yellow pattern instead of being discharged thereon. The ageing operation oper ates by destroying the zinc formaldehyde sul- 35 phoxylate and so permits fixation of the green pattern over the yellow pattern.

Inthe following paragraphs A to F there are indicated in a more detailed manner some of the methods by which pattern effects may be pro- 40 duced in accordance with the invention, which however is not restricted thereto.

To a cellulose acetate fabric is applied a ground colouration dischargeable by both zinc formaldehyde sulphoxylate and stannous chloride discharges. It is then printed with a zinc formaldecolouring matters resistant to zinc formaldehyde sulphoxylate, dried, cover printed with a stannous chloride discharge containing dyestuffs resistant to stannous chloride but dischargeable by zinc formaldehyde sulphoxylate, aged, steamed if 5 necessary, and washed ofi. A white or coloured discharge is obtained on a dyed ground with the coloured pattern produced by the cover printing appearing only on the ground colouration.

A cellulose acetate fabric coloured with a ground colouration as in A above is printed with a stannous chloride discharge containing dyestuffs resistant to stannous chloride but dischargeable by zinc formaldehyde sulphoxylate. It is then dried, aged, and if desired washed off. It is then cover printed with a zinc formaldehyde sulphoxylate discharge containing dyestuffs resistant to zinc formaldehyde sulphoxylate, aged, steamed if necessary, and washed off. A coloured discharge is obtained on a dyed ground with the pattern produced by the cover print both on the ground colour and on the pattern produced by the stannous chloride discharge. I

, ageing and chromin'g.

l Acellulose acetate fabric is printed with a resist composition containing zinc formaldehyde sulphoxylate, with or without dyestuffs which are resistant to zinc formaldehyde sulphoxylate. It is then dried,coverprintedwith a second composition containing an aniline black resist agent, e.g. an alkali, together with dyestuffs resistant thereto but not resistant to zinc formaldehydesulphoxylate, and dried and padded with an aniline black liquor, aged, steamed if necessary, chromed and washed off. White and/or coloured resists on a black ground with'a second coloured resist appearing on the ground only are obtained. If desired the aniline black liquor may .be padded on to the material prior to printing the resists but before ageing and chroming.

black ground ,with white or coloured cover resists appearing both on the black ground and on the first mentioned coloured resist. If desired the aniline black liquor may be padded on to the material prior to printing the resists but before A cotton fabric is coloured with colouring matters dischargeable both by sulphoxylate discharges and by stannous discharges, and prepared with a suitable mordant, e. g. tannic acid orthe substance sold under the trade name Katanol O, the wordKatanol being a registered trade-mark. It is then printed with a composition containing sodium formaldehyde sulphoxylate with or without dyestuffs resistant thereto, dried, and cover printed with a stannous chloride discharge containing dyestuffs, e. g.basic dyestuffs resistant to stannous chloride but dischargeable with sodium formaldehyde sulphoxylate. The fabric is finally aged, and where a tannic acid mordant has been employed, the latter is fixed with tartar emetic. White or coloured discharges are obtained on a dyed ground with other coloured discharges appearing on the ground only and not on the first mentioned discharges.

A cotton fabric is dyed and prepared as in E above, printed with a stannous chloride discharge containing dyestuffs resistantto stannous chloride but discharged by zinc formaldehyde sulphoxystroyed before the application of the second dis- I charge composition.

A cellulose acetate fabric coloured with a ground colour as in A above is printed with a discharge composition containing zinc formaldehyde sulphoxylate with or without dyestuffs resistant to zinc formaldehyde sulphoxylate, dried, aged, and washed off if desired. It is then cover printed with a stannous chloride discharge containing dyestuffs resistant to stannous chloride, aged, steamed if necessary, and washed off. White or coloured discharges are obtained on a dyed ground, the pattern produced by the cover print appearing both on the ground and on the zinc formaldehyde sulphoxylate discharge. Since the intermediate drying and ageing destroys the zinc formaldehyde sulphoxylate the colour produced by thecover print is superimposed on that of the first print where the two prints overlap. For example a yellow cover print on a blue discharge print will give a green colour in the overlapping areas.

A cotton fabric is coloured with a ground colour and prepared with mordants as in E above, and is printed with a composition containing sodium formaldehyde sulphoxylate with or without dyestuffs resistant to sodium formaldehyde sulphoxylate. It is then dried, aged, washed if .necessary, and cover printed with a stannous chloride discharge containing dyestufis resistant to stannous chloride but discharged by sodium formaldehyde sulphoxylate. It is then again aged,.fixed with tartar emetic if prepared with tannic acid, and washed. White or coloured discharges are obtained on a dyed ground with other discharges appearing both on the ground and on the first mentioned discharges. In this case the colour of the second discharge is superimposed on that of the first discharge, if any,"since the intermediate ageing destroys sodium formaldehyde sulphoxylate, For

example if the two discharges are respectively 45 yellow and blue, a green is obtained where the two overlap.

A wide range of dyestuffs, dischargeable both by stannous compounds and sulphoxylates, is

" available for producing the desired dischargeable ground colourations. In the case of cellulose ester and ether materials mention may be made of the insoluble and difl'icultly soluble colouring matters of the azo and nitro diarylamine series commonly employed in thecolouration of cellulose ester materials. Examples of such colouring matters are benzene-azo-l -naphthalene-4 azo- 4'-hydroxy benzene, para-nitrobenz'ene-azo-ldiphenylamine, 4-nitrobenzene-1'-azo-4'-amino- 3'6 dimethylbenzene, 4 nitro-Z-methoxy-benzene-1-azo-4"-dimethyiaminobenzene, 4-nitro-2- methoxy-benzene-l-azo-4'-diethylaminobenzene, 2 :i-dinitro -benzene-azo -4 -diethylaminobenzene, the azo dyes from dinitro-o-anisidine or paranitro-o-anisidine and w oxyethvl a naphthylamine, and -o-methoxy-benzene-azo-a-naphthylamine diazotized and developed on the material with fl-oxynaphthoic acid.

For the colouration of the discharges any suitable colouring matter may be employed. As examples of colouring matters resistant to sulphoxylates particular mention, may be made of vat dyestufls applied in reduced form either as alkali i For resisting stannous discharges but not sulphoxylate discharges use may be made of di-or triarylmethane dyestuffs or others of the basic dyestuff series, for example Malachite green crystals, Acronol green BS, Magenta crystals, Rhoduline blue B, Rosol scarlet G extra, Setocyanine and Setoglaucine, Brilliant Rhoduline purple R and Turquoise blue BB. Most of these have good direct aflinity for cellulose esters and ethers and may be used on cotton with the aid of tannic acid, or the basic dye mordants obtainable by sulphurizlng phenols, e. g. the product sold under the registered trade-mark Katanol.

Dyestuffs having a carboxyl group or a single sulphonic group as substituents, such for example as dyestuffs of the anthraquinone or pyrazolone series having a carboxyl group or a single sulphonic group as substituents, may be employed for colouring both cellulose derivative fibres and animal fibres and are valuable for colouring discharge preparations for the local colouration of such fibres in mixed materials containing cellulose deriyative and animal fibresl Thus for example discharge preparations for printing on mixed materials consisting of cellulose acetate and silk may be coloured with Solway Ultra blue B S, Modern yellow powder, or the dyestuff ob tained by diazotizing anthranilic acid and coupling with phenyl methyl pyrazolone.

The following examples illustrate the invention without being in any way limitative Example 1 A cellulose acetate fabric is dyed a red shade with l-nitro-2-methoxybenzene1-azol -diethylaminobenzene, which is a dyestufi dischargeable both by sulphoxylates and by stannous discharges, and printed in a floral design with the following composition:-

Grams 20% aqueous paste of the dyestuff parahydroxy-benzene-azo-1-phenyl-3 -methyl- 5 -pyrazolone 15 Methylated spirits Gum arabic 1:1 55

Water 1 5 Decrolin sol. conc After printing, the fabric is dried and immediately cover-printed with a design comprising numerous small spots with a composition of the following constitution After cover-printing, the fabric is aged, and, if desired, gassed and steamed further in order to fix colouring matter, and is then washed, dried and finished as desired. A yellow floral design on a red ground is obtained with a green spotted pattern on the ground only.

Example 2 A cellulose acetate fabric is dyed as in Example 1 and then printed in a floral design with the following composition:-

' Grams Malachite green crystals 1.5 Methylated spirits 10.0 5 Sodium sulphocyanide 50% 5.0 Citric acid 1.0 Water 12.5 Gum arabic 1:1 60.0 Stannous chloride 10.0 10

After printing, the fabric is dried and coverprinted with a design comprising numerous small 15 spots with a composition containing:-

Grams aqueous paste of the dyestuff parahydroxy-benzene-azo-1-phenyl-3 -methyl- 20 5-pyrazolone 5 Methylated spirits 10 Gum arabic 1:1 55

Water 5 Decrolin sol. conc 15 The fabric is then dried, aged and steamed and washed and finished as requisite. A green floral design is obtained on a red ground with a further spotted design in yellow which appears both on the ground and where the printed and coverprinted designs overlap.

Sodium acetate 25 Sodium formaldehyde sulphoxylate 10 After drying, the fabric is immediately coverprinted in an all-over pattern of fine spots with the following composition:-

Grams Malachite green crystals 1.5 Methylated spirits 10.0 Water -4 13.5 Gum arabic 1:1 50.0 Sodium acetate 25.0

andis then dried and aged and padded with a liquor containing:-

Grams Aniline hydrochloride 120 Acetic acid 24 Methylated spirits 96 Water -2 350 10% tragacanth thickening; 250 7 Sodium chloride '77 Cupric chloride 3 Water 80 The fabric is finally dried, aged, gassed and steamed if desired, chromed, washed, dried and subjected to any other desired finishing treatment. A yellow floral design is obtained on a black ground with a further spotted green design on the ground only.

The following example illustrates the modification of the invention wherein the first discharging agent is destroyed before the second discharge composition is applied:-

Example 4 A cellulose acetate fabric is dyed and printed as in Example 1 except that after printing but before overprinting it is subjected to an ageing treatment. The efiect obtained is a yellow floral design on a red ground with a green spotted fore moist heat treatment, both a composition comprising a discharging agent for the said ground color and a coloring matter resistant to said discharging agent, and a composition comprising an agent whichwill discharge the ground color-and also the coloring matter of the other composition, so that at least part of the second mentioned discharge composition falls on areas covered by the first, and thereafter subjecting the materials to a moist heat treatment to eflect discharge and fix coloring matters. 5

2. Process for the production of colored pattern efiects on textile materials by discharge of ground color, which comprises applying to selected areas a composition comprising a, discharging agent for the said ground color and a coloring matter resistant to said discharging agent, and, without removing the said discharge composition, applying a second composition comprising an agent which will discharge the ground color and also the coloring matter of the other composition, so that at least part of the second mentioned discharge composition falls on areas covered by the first.

3. Process for the production of colored pattern eflects on textile materials by discharge of ground color which comprises applying to selected areas a composition comprising a discharging agent for the said ground color and a coloring matter resistant to said discharging agent and, without intermediate treatment, applying a second composition comprising an agent which will discharge the ground color and also the coloring matter of the other composition, so that at least part of the second mentioned discharge composition falls on areas covered by the first.

GEORGE HOLLAND ELLIS. JOHN ALLAN. 

